In "Chuck Versus the Nacho Sampler" Hannah turns up in Burbank and accepts Chuck's offer to work for the Buy More's Nerd Herd team but Chuck's efforts to train her are repeatedly frustrated by his current mission. Hannah herself is unknowingly caught up in another operation during her first Nerd Herd service call; after Chuck's team steals a mask of Alexander the Great, a Ring operative uses her as bait to force Chuck to return the mask, and the cyclosarin gas being smuggled within. Afterwards, she and Chuck begin a relationship, but Chuck breaks up with her to protect her from the lies he would have to tell her as part of his double life.

In her first appearance in "Chuck Versus First Class", Hannah seems to have a unique relationship with Chuck Bartowski upon their meeting. They seem to be flirty and she is curious about Chuck. She even offers to show Chuck a tour of Paris. Fans speculate that she may potentially be a new love interest for Chuck.

In "Chuck Versus the Mask" Hannah reveals that she has feelings for Chuck when she is unknowingly helping him with one of his spy missions. When Ellie and Morgan, become suspicious about Chuck's frequent disappearances from work, they find Hannah macking on Chuck in the Home Theater room, much to the dismay of Morgan, who has feelings for Hannah. Hannah and Chuck begin dating, however once Chuck realizes that he will have to lie to her about his spy life, he chooses to break up with her to protect her feelings. Hannah becomes very upset, thinking Chuck lied to her just so he could sleep with her. She quits the Buy More after their break up and is not seen again.